LITHIUM-CONTAINING GARNET CRYSTAL BODY, METHOD FOR PRODUCING SAME, AND ALL-SOLID-STATE LITHIUM ION SECONDARY BATTERY

Abstract

Provided is a high-density lithium-containing garnet crystal body. The lithium-containing garnet crystal body has a relative density of 99% or more, belongs to a tetragonal system, and has a garnet-related type structure. A method of producing a Li.sub.7La.sub.3Zr.sub.2O.sub.12 crystal, which is one example of this lithium-containing garnet crystal body, includes melting a portion of a rod-like raw material composed of polycrystalline Li.sub.7La.sub.3Zr.sub.2O.sub.12 belonging to a tetragonal system while rotating it on a plane perpendicular to the longer direction and moving the melted portion in the longer direction. The moving rate of the melted portion is preferably 8 mm/h or more but not more than 19 mm/h. The rotational speed of the raw material is preferably 30 rpm or more but not more than 60 rpm. By increasing the moving rate of the melted portion, decomposition of the raw material due to evaporation of lithium can be prevented and by increasing the rotational speed of the raw material, air bubbles can be removed.

Claims

1. A lithium-containing garnet crystal body having a relative density of 99% or more, belonging to a tetragonal system, and having a garnet-related type structure.

2. The lithium-containing garnet crystal body according to claim 1, comprising a Li.sub.7La.sub.3Zr.sub.2O.sub.12 crystal.

3. The lithium-containing garnet crystal body according to claim 1, wherein the relative density is 100%.

4. The lithium-containing garnet crystal body according to claim 1, which satisfies at least one of the following conditions (1) and (2): (1) the Nyquist plot of the crystal body by ac impedance measurement does not show a resistance component due to crystal grain boundaries but only a resistance component of a material itself; and (2) in X-ray diffraction measurement, neutron diffraction measurement, or electron diffraction measurement using a single crystal, a ring-shaped diffraction spot appears in a diffraction pattern.

5. The lithium-containing garnet crystal body according to claim 1, having lattice constants of 1.3052 nm≦a≦1.31323 nm and 1.26702 nm≦c≦1.3024 nm.

6. The lithium-containing garnet crystal body according to claim 5, having Li on four kinds of ion sites, that is, 8a site, 16f site, 32g site, and 16e site.

7. A method of producing a Li.sub.7La.sub.3Zr.sub.2O.sub.12 crystal having a garnet-related type structure, comprising melting at least a portion of a raw material composed of polycrystalline Li.sub.7La.sub.3Zr.sub.2O.sub.12 to form a melted portion and moving the melted portion, wherein: a moving rate of the melted portion is 8 mm/h or more, and the Li.sub.7La.sub.3Zr.sub.2O.sub.12 crystal has a relative density of 99% or more.

8. The method of producing a Li.sub.7La.sub.3Zr.sub.2O.sub.12 crystal according to claim 7, wherein the moving rate is 8 mm/h or more but not more than 19 mm/h.

9. The method of producing a Li.sub.7La.sub.3Zr.sub.2O.sub.12 crystal according to claim 7, wherein a portion of the raw material in rod form is melted while rotating the raw material on a plane perpendicular to the longer direction; and the melted portion is moved in the longer direction.

10. The method of producing a Li.sub.7La.sub.3Zr.sub.2O.sub.12 crystal according to claim 9, wherein the raw material is rotated at a rotational speed of 30 rpm or more.

11. The method of producing a Li.sub.7La.sub.3Zr.sub.2O.sub.12 crystal according to claim 10, wherein the rotational speed of the raw material is 30 rpm or more but not more than 60 rpm.

12. The method of producing a Li.sub.7La.sub.3Zr.sub.2O.sub.12 crystal according to claim 7, wherein the polycrystalline Li.sub.7La.sub.3Zr.sub.2O.sub.12 and the Li.sub.7La.sub.3Zr.sub.2O.sub.12 crystal belong to a tetragonal system.

13. The method of producing a Li.sub.7La.sub.3Zr.sub.2O.sub.12 crystal according to claim 7, wherein the Li.sub.7La.sub.3Zr.sub.2O.sub.12 crystal has a relative density of 100%.

14. The method of producing a Li.sub.7La.sub.3Zr.sub.2O.sub.12 crystal according to claim 7, wherein melting of the raw material and moving of the melted portion are performed in a dry air atmosphere.

15. An all-solid-state lithium ion secondary battery comprising a positive electrode, a negative electrode, and a solid electrolyte, wherein the solid electrolyte has the lithium-containing garnet crystal body as claimed in claim 1.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0012] FIG. 1 is a single crystal X-ray diffraction pattern of a tetragonal system Li.sub.7La.sub.3Zr.sub.2O.sub.12 crystal having a plurality of domains.

[0013] FIG. 2 is an appearance photograph of the tetragonal system Li.sub.7La.sub.3Zr.sub.2O.sub.12 crystal prepared by the FZ method of Example.

[0014] FIG. 3 is a single crystal X-ray diffraction pattern of the tetragonal system Li.sub.7La.sub.3Zr.sub.2O.sub.12 crystal prepared by the FZ method of Example.

[0015] FIG. 4 is a schematic view showing the garnet-related type structure of the tetragonal system Li.sub.7La.sub.3Zr.sub.2O.sub.12 crystal prepared by the FZ method of Example.

[0016] FIG. 5 is a powder X-ray diffraction pattern of the tetragonal system Li.sub.7La.sub.3Zr.sub.2O.sub.12 crystal prepared by the FZ method of Example.

[0017] FIG. 6 is a Nyquist plot of the tetragonal system Li.sub.7La.sub.3Zr.sub.2O.sub.12 crystal prepared by the FZ method of Example.

[0018] FIG. 7 is an appearance photograph of a tetragonal system Li.sub.7La.sub.3Zr.sub.2O.sub.12 crystal obtained by the CZ method of Example.

[0019] FIG. 8 is a powder X-ray diffraction pattern of the tetragonal system Li.sub.7La.sub.3Zr.sub.2O.sub.12 crystal prepared by the CZ method of Example.

DESCRIPTION OF EMBODIMENTS

[0020] The lithium-containing garnet crystal body, method of producing a Li.sub.7La.sub.3Zr.sub.2O.sub.12 crystal, and all-solid-state lithium ion secondary battery according to the present invention will hereinafter be described in detail based on Embodiment and Example. It is to be noted that an overlapping description will be omitted as needed.

[0021] The lithium-containing garnet crystal body according to the embodiment of the present invention has a relative density of 99% or more, belongs to a tetragonal system, and has a garnet-related type structure. The relative density can be calculated by measuring an external shape of a thin slice of the crystal, calculating an apparent volume, and dividing an apparent density calculated from the measured mass by a true density obtained from single crystal X-ray structural analysis results. The lithium-containing garnet crystal body of the present embodiment has preferably a higher relative density. All the crystal domains of the lithium-containing garnet crystal of the present embodiment do not necessarily face the same direction.

[0022] When a lithium-containing garnet crystal body tends to have crystal domains aligned in one direction, a diffraction spot is observed as a clear spot in the X-ray diffraction measurement using a single crystal as shown later in FIG. 3. FIG. 1 is a single crystal X-ray diffraction pattern of a tetragonal system Li.sub.7La.sub.3Zr.sub.2O.sub.12 crystal having crystal domains not aligned in one direction and prepared in a test. This sample is a tetragonal system Li.sub.7La.sub.3Zr.sub.2O.sub.12 single crystal prepared by moving the melted portion at 100 mm/h. Too high cooling rate of the melted portion has prevented the crystal from growing to having crystal domains aligned in one direction in the sample.

[0023] When the crystal domains of the lithium-containing garnet crystal body are not aligned in one direction, diffraction spots are complicated or diffractions from various domains overlap with each other to form a diffraction spot shaped like a ring as shown in FIG. 1. Examples of the lithium-containing garnet crystal body of the present embodiment include Li.sub.7La.sub.3Zr.sub.2O.sub.12 crystal, tetragonal system Li.sub.7La.sub.3Hf.sub.2O.sub.12 crystal, and tetragonal system Li.sub.7La.sub.3Sn.sub.2O.sub.12 crystal.

[0024] A polycrystal body has difficulty in having an increased relative density so that in ac impedance measurement, many voids in the polycrystal body are reflected on the measurement results. The Nyquist plot, by AC impedance measurement, of the Li.sub.7La.sub.3Zr.sub.2O.sub.12 polycrystal body which has already been reported shows two resistance components, that is, a resistance component due to crystal grain boundaries and a resistance component of the material itself (refer to Non-patent Document 1). On the other hand, the Nyquist plot of the lithium-containing garnet crystal body of the present embodiment shows not a resistance component due to crystal grain boundaries but only a resistance component of the material itself, as shown later in FIG. 6. In the single-crystal X-ray diffraction measurement, neutron diffraction measurement, or electron diffraction measurement of the lithium-containing garnet crystal body of the present embodiment, a ring-shaped crystal spot appears in the diffraction pattern as shown later in FIG. 3.

[0025] The lithium-containing garnet crystal body of the present invention has excellent lithium ion conductivity so that it can be used for an electrolyte of an all-solid-state lithium ion second battery. This means that the all-solid-state lithium ion secondary battery of the present invention has a positive electrode, a negative electrode, and a solid electrolyte and the solid electrolyte is composed of the lithium-containing garnet crystal body of the present invention, for example, a Li.sub.7La.sub.3Zr.sub.2O.sub.12 crystal having a relative density of 99% or more, belonging to a tetragonal system, and having a garnet-related type structure. A Li.sub.7La.sub.3Zr.sub.2O.sub.12 crystal having a relative density of 100%, that is, an essential Li.sub.7La.sub.3Zr.sub.2O.sub.12 single crystal has particularly excellent lithium ion conductivity.

[0026] A method of producing a Li.sub.7La.sub.3Zr.sub.2O.sub.12 crystal according to the embodiment of the present invention is a method of melting at least a portion of a raw material composed of polycrystalline Li.sub.7La.sub.3Zr.sub.2O.sub.12 to form a melted portion and moving the melted portion to produce a Li.sub.7La.sub.3Zr.sub.2O.sub.12 crystal having a garnet-related type structure. The moving rate of the melted portion is 8 mm/h more and the relative density of the Li.sub.7La.sub.3Zr.sub.2O.sub.12 crystal is 99% or more. The method of producing a Li.sub.7La.sub.3Zr.sub.2O.sub.12 crystal according to the present embodiment is a method of growing a Li.sub.7La.sub.3Zr.sub.2O.sub.12 crystal from a melt of the raw material, more specifically, the floating zone (FZ) method, Czochralski (CZ) method, Bridgman method, Pedestal method or the like corresponds to it. A suitable method may be selected from these methods, depending on the size, shape, or the like of the Li.sub.7La.sub.3Zr.sub.2O.sub.12 crystal to be produced.

[0027] In production of a Li.sub.7La.sub.3Zr.sub.2O.sub.12 crystal by the FZ method, a rod-like raw material is partially melted while rotating it on a plane perpendicular to its longer direction and moving the melted portion in the longer direction to grow the Li.sub.7La.sub.3Zr.sub.2O.sub.12 crystal. The rod-like raw material composed of polycrystalline Li.sub.7La.sub.3Zr.sub.2O.sub.12 is prepared as follows. First, a lithium compound, a lanthanum compound, and a zirconium compound are weighed to give a Li:La:Zr mole ratio of 7-8:3:2 in consideration of evaporation of lithium at high temperature.

[0028] The lithium compound is not particularly limited insofar as it contains lithium and examples include Li.sub.2O and Li.sub.2CO.sub.3. The lanthanum compound is not particularly limited insofar as it contains lanthanum and examples include La.sub.2O.sub.3 and La(OH).sub.3. The zirconium compound is not particularly limited insofar as it contains zirconium and examples include ZrO.sub.2 and ZrCl.sub.4. It is also possible to use compounds containing two or more of lithium, lanthanum, and zirconium, for example, La.sub.2Zr.sub.2O.sub.7 and Li.sub.2ZrO.sub.3 and weigh them to give a Li:La:Zr mole ratio of 7-8:3:2.

[0029] Next, the compounds thus weighed are mixed. A mixing method is not particularly limited insofar as it can uniformly mix the compounds. For example, they may be mixed in a wet or dry system by a mixing machine such as mixer. After the resulting mixture is poured in a crucible with a lid, it is temporarily calcined at from 900° C. to 1000° C., preferably from 930° C. to 990° C. to obtain a polycrystalline Li.sub.7La.sub.3Zr.sub.2O.sub.12 powder to be served as a raw material. The product obtained by temporary calcining is preferably ground, mixed, and calcined in repetition. The resulting polycrystalline Li.sub.7La.sub.3Zr.sub.2O.sub.12 powder belongs to a tetragonal system.

[0030] Next, in order to facilitate molding, the polycrystalline Li.sub.7La.sub.3Zr.sub.2O.sub.12 powder thus obtained is ground to reduce its particle size. A grinding method is not particularly limited insofar as it can grind the powder into small-sized ones. For example, the powder may be wet- or dry-ground using a grinder such as planetary ball mill, pot mill, or beads mill. After the ground product is poured in a rubber tube, it is formed into a rod by isostatic pressing. Next, the product thus formed is calcined at a temperature of from about 800° C. to 1300° C., preferably from 900° C. to 1100° C. to obtain a rod-like polycrystalline Li.sub.7La.sub.3Zr.sub.2O.sub.12 raw material. This rod-like polycrystalline Li.sub.7La.sub.3Zr.sub.2O.sub.12 belongs to a tetragonal system.

[0031] The resulting rod-like polycrystalline Li.sub.7La.sub.3Zr.sub.2O.sub.12 raw material belonging to a tetragonal system is melted in an infrared condensing furnace and then quenched. As a result, a Li.sub.7La.sub.3Zr.sub.2O.sub.12 crystal having a garnet-related type structure is produced. The Li.sub.7La.sub.3Zr.sub.2O.sub.12 crystal thus produced belongs to a tetragonal system. Decomposition of the raw material due to evaporation of lithium can be prevented by increasing the moving rate of the melted portion to 8 mm/h or more. The moving rate of this melted portion is preferably 8 mm/h or more but not more than 19 mm/h.

[0032] At the melted portion, evaporation of lithium is accompanied by generation of air bubbles, but these air bubbles can be removed by increasing the rotational speed of the rod-like polycrystalline Li.sub.7La.sub.3Zr.sub.2O.sub.12 raw material to 30 rpm or more. The rotational speed of the raw material is preferably 30 rpm or more but not more than 60 rpm. Melting of the raw material and moving of the melted portion are preferably performed in a dry air atmosphere. In such a manner, a high density Li.sub.7La.sub.3Zr.sub.2O.sub.12 crystal having a relative density of 99% or more can be produced. A Li.sub.7La.sub.3Zr.sub.2O.sub.12 crystal having a relative density of 100% can also be produced.

[0033] Production of a Li.sub.7La.sub.3Zr.sub.2O.sub.12 crystal by the CZ method is performed in the following procedure. First, a raw material polycrystalline Li.sub.7La.sub.3Zr.sub.2O.sub.12 is poured in a crucible and is melted by heating. Then, a seed crystal is dipped in a melt of the raw material and then, it is pulled up while rotating. It is presumed that by increasing the moving rate of the melted portion, that is, a pulling rate of the seed crystal to 8 mm/h or more, evaporation of lithium is suppressed and a high density Li.sub.7La.sub.3Zr.sub.2O.sub.12 crystal can be obtained.

EXAMPLE

[0034] 1. Production of Li.sub.7La.sub.3Zr.sub.2O.sub.12 Crystal by FZ Method

[0035] (1) Preparation of Polycrystalline Li.sub.7La.sub.3Zr.sub.2O.sub.12 Powder

[0036] First, as starting raw materials, 10.1175 g of lithium carbonate Li.sub.2CO.sub.3 (product of RARE METALLIC, purity: 99.99%), 17.4606 g of lanthanum oxide La.sub.2O.sub.3 (product of RARE METALLIC, purity: 99.99%), and 8.7648 g of zirconium oxide ZrO.sub.2 (product of RARE METALLIC, purity: 99.99%) were poured in an agate mortar and they were uniformly mixed by a wet process using ethanol. As lanthanum oxide, that temporarily calcined at 900° C. in advance was used. Then, an alumina crucible with lid (product of Nikkato, C5 model) was filled with 36 g of the resulting mixture. The crucible was placed in a box type electric furnace (product of Yamato Scientific, FP100 model) and the mixture was temporarily calcined at 950° C. for 5 hours to obtain a powder. The powder thus obtained was ground in a mortar and then calcining at 980° C. for 10 hours was performed twice to prepare a polycrystalline Li.sub.7La.sub.3Zr.sub.2O.sub.12 powder.

[0037] The resulting polycrystalline Li.sub.7La.sub.3Zr.sub.2O.sub.12 powder was then ground. More specifically, grinding was performed by filling a 45-mL zirconium grinding container with 30 g of the resulting polycrystalline Li.sub.7La.sub.3Zr.sub.2O.sub.12 powder, 50 g of zirconia balls having a diameter of 5 mm, and 14 mL of ion exchanged water and rotating it in a planetary ball mill (product of Fritsch/Germany, model P-6) for 300 minutes in total at revolution speed of 200 rpm. After grinding, the polycrystalline powder was dried at 100° C. for 24 hours and classified through a sieve with a 250-μm opening.

[0038] (2) Preparation of Rod-Like Polycrystalline Li.sub.7La.sub.3Zr.sub.2O.sub.12

[0039] Rod-like polycrystalline Li.sub.7La.sub.3Zr.sub.2O.sub.12 was prepared in the following procedure by using the polycrystalline Li.sub.7La.sub.3Zr.sub.2O.sub.12 powder that had passed the sieve in the above step. First, a mold made of rubber was filled with 26 g of the polycrystalline Li.sub.7La.sub.3Zr.sub.2O.sub.12 powder, followed by deaeration. The mold was then hermetically sealed, put in water, and retained in water at 40 MPa for 5 minutes. After the pressure of water was reduced, the molded product was taken out from the mold. The molded product had a columnar shape having a diameter of 1.2 cm and a height of 7 cm. Then, the molded product was calcined at 1150° C. for 8 hours in a box-type electric furnace (product of DENKEN, Model No. KDF009). The calcined product thus obtained had a rod-like and nearly columnar shape having a width of 1 cm and a length of 7 cm and it had a mass of 26 g. The powder X-ray diffraction pattern by a powder X-ray diffraction apparatus (product of Rigaku, Smart Lab) revealed that the calcined product was polycrystalline Li.sub.7La.sub.3Zr.sub.2O.sub.12 belonging to a tetragonal system.

[0040] (3) Growth of Li.sub.7La.sub.3Zr.sub.2O.sub.12 Crystal

[0041] First, the rod-like polycrystalline Li.sub.7La.sub.3Zr.sub.2O.sub.12 raw material obtained by the above step was placed in a four ellipsoidal infrared condensing heating furnace (FZ furnace) (product of Crystal System, FZ-T-10000H model) equipped with a 100-kW halogen lamp and atmosphere was changed to dry air one. Next, the rod-like polycrystalline Li.sub.7La.sub.3Zr.sub.2O.sub.12 raw material was heated at an output of 51.9% while rotating it on a plane perpendicular to the longer direction at 45 rpm. After a while, a portion of the polycrystalline Li.sub.7La.sub.3Zr.sub.2O.sub.12 raw material was melted to form a melted portion. An installation base of the polycrystalline Li.sub.7La.sub.3Zr.sub.2O.sub.12 raw material was then lowered at a moving rate of 8 mm/h and 19 mm/h to grow a Li.sub.7La.sub.3Zr.sub.2O.sub.12 crystal. The appearance of the Li.sub.7La.sub.3Zr.sub.2O.sub.12 crystal (which may hereinafter be called “Sample 1”) obtained by setting the moving rate of the installation base to 19 mm/h is shown in FIG. 2.

[0042] The structure of Sample 1 was analyzed using a single crystal X-ray diffraction analyzer (product of Rigaku Corporation, R-AXIS RAPID-II). The X-ray diffraction pattern of Sample 1 is shown in FIG. 3. As shown in FIG. 3, a clear diffraction point was measured. Diffraction intensity data were collected using a program RAPID AUTO attached to the single crystal X-ray diffraction analyzer and the crystal structure of Sample 1 was investigated using a crystal structure analysis program Jana2006. As a result, Sample 1 was found to belong to a tetragonal system. Sample 1 was cut by a diamond cutter to obtain four slices having a thickness of 0.1 mm. The relative density of them was calculated by the above-described method. As a result, the relative densities of them were found to be 99.0%, 99.4%, 99.7%, and 100%, respectively.

[0043] The lattice constants of Sample 1 were determined, using the least squares method, from the reflection observed in single crystal X-ray diffraction measurement. As a result, they were found to be a=1.3061 nm±0.0009 nm and c=1.3012 nm±0.0012 nm. The lattice constants revealed that Sample 1 was a lithium composite oxide having a garnet-related type structure. The lattice constants also revealed that compared with the crystal lattice of tetragonal system Li.sub.7La.sub.3Zr.sub.2O.sub.12 so far reported, Sample 1 was a novel tetragonal system garnet-related type structure Li.sub.7La.sub.3Zr.sub.2O.sub.12 having a crystal lattice closer to that of a cubic system. Even when the rotational speed of the polycrystalline Li.sub.7La.sub.3Zr.sub.2O.sub.12 raw material was set at 30 rpm and 60 rpm, a Li.sub.7La.sub.3Zr.sub.2O.sub.12 crystal having a relative density of 99% or more, belonging to a tetragonal system, and having a garnet related type structure was obtained.

[0044] The results of the crystal structure analysis of Sample 1 using a crystal structure analysis program Jana2006 based on the diffraction intensity data collected using a program RAPID AUTO attached to the single crystal X-ray diffraction analyzer are shown in FIG. 4. Compared with the tetragonal system garnet-related type structure so far reported, Sample 1 is different in arrangement of lithium ions and occupation state of lithium sites in the crystal structure. Tetragonal system Li.sub.7La.sub.3Zr.sub.2O.sub.12 so far reported has three lithium ion sites (8a site, 16f site, and 32g site) in the crystal structure and their occupancies are 100%, while Sample 1 has five, but four in the number of kinds, lithium ion sites (8a site, 16f site, two 32g sites, and 16e site) in the crystal structure and their occupancies were from 30 to 50%.

[0045] This means that Sample 1 had Li on four kinds of ion sites, that is, 8a site, 16f site, 32g site, and 16e site. The arrangement of lithium ions changes and becomes close to the arrangement of lithium ions of Li.sub.7La.sub.3Zr.sub.2O.sub.12 having a cubic system garnet-related type structure so far reported. It is therefore presumed that the lattice constants of Sample 1 become close to those of a cubic system. The above-described crystal structure analysis results are said to be appropriate because an R factor, indicating the reliability of the crystal structure analysis, is 7.46%. FIG. 5 shows the results of powder X-ray diffraction measurement of Sample 1 after grinding. The powder X-ray diffraction pattern of Sample 1 was similar to that of the Li.sub.7La.sub.3Zr.sub.2O.sub.12 having a tetragonal system garnet-related type structure so far reported. The lattice constants calculated from the results of the powder X-ray structure analysis were a=1.31270 nm±0.00002 nm and c=1.26882 nm±0.00003 nm.

[0046] (4) Measurement of Lithium Ion Conductivity of Li.sub.7La.sub.3Zr.sub.2O.sub.12 Crystal

[0047] First, Sample 1 was cut into a columnar thin slice having a diameter of about 1.0 cm and a thickness of about 0.19 cm. Then, a rectangular parallelepiped shaped gold having a square bottom surface 0.18 cm on a side and a thickness of 40 nm was sputtered onto both surfaces of the thin slice to form an electrode. Impedance of Sample 1 was measured at 25° C. in a nitrogen atmosphere by the ac impedance method (apparatus used for measurement: Solarton, 1260). The Nyquist plot at that time is shown in FIG. 6. The lithium ion conductivity found from the Nyquist plot shown in FIG. 6 was 4.6×10.sup.−5 S/cm.

[0048] 2. Preparation of Li.sub.7La.sub.3Zr.sub.2O.sub.12 Crystal by CZ Method

[0049] (1) Preparation of Polycrystalline Li.sub.7La.sub.3Zr.sub.2O.sub.12 Powder

[0050] A sieved polycrystalline Li.sub.7La.sub.3Zr.sub.2O.sub.12 powder was prepared in a manner similar to that described above in “preparation of polycrystalline Li.sub.7La.sub.3Zr.sub.2O.sub.12 powder” in “production of Li.sub.7La.sub.3Zr.sub.2O.sub.12 crystal by FZ method”.

[0051] (2) Growth of Li.sub.7La.sub.3Zr.sub.2O.sub.12 Crystal

[0052] First, a cylindrical iridium container having an inner diameter of 2.6 cm and a depth of 2.8 cm was filled with 38 g of the polycrystalline Li.sub.7La.sub.3Zr.sub.2O.sub.12 powder obtained in the above step. The iridium container was then placed in a single crystal pulling furnace (CZ furnace) (product of TECHNO SEARCH, TCH-3) equipped with high-frequency induction heating function. A tungsten rod 0.8 mm long was placed in a pulling unit and the CZ furnace was adjusted to have a dry nitrogen atmosphere. Next, the high frequency output was increased gradually and the iridium container was heated continuously at an output of 76.2%. After a while, the Li.sub.7La.sub.3Zr.sub.2O.sub.12 powder in the iridium container was melted.

[0053] After the resulting tungsten rod was put in the melted portion of Li.sub.7La.sub.3Zr.sub.2O.sub.12 while rotating it at 10 rpm on a plane perpendicular to the longer direction, the tungsten rod was elevated at a moving rate of 10 mm/h to grow a Li.sub.7La.sub.3Zr.sub.2O.sub.12 crystal. The appearance of the Li.sub.7La.sub.3Zr.sub.2O.sub.12 crystal thus grown (which may hereinafter be called “Sample 2”) is shown in FIG. 7. The results of powder X-ray diffraction measurement of Sample 2 after grinding are shown in FIG. 8.

[0054] The powder X-ray diffraction pattern of Sample 2 was similar to that of Li.sub.7La.sub.3Zr.sub.2O.sub.12 having a tetragonal system garnet-related type structure so far reported. The lattice constants calculated based on the results of powder X-ray structure analysis were a=1.31322 nm±0.00001 nm and c=1.26703 nm±0.00001 nm. The results of the single crystal X-ray diffraction measurement and the powder X-ray structure analysis of the Li.sub.7La.sub.3Zr.sub.2O.sub.12 crystal produced by the FZ method and the results of the powder X-ray structure analysis of the Li.sub.7La.sub.3Zr.sub.2O.sub.12 crystal produced by the CZ method used in combination show that the lattice constants of the Li.sub.7La.sub.3Zr.sub.2O.sub.12 crystal are 1.3052 nm≦a≦1.31323 nm and 1.26702 nm≦c≦1.3024 nm.

INDUSTRIAL APPLICABILITY

[0055] The lithium-containing garnet crystal body of the present invention can be used as a material of a solid electrolyte of all-solid-state lithium ion secondary batteries and the like.